Process of manufacturing stannic chlorid from materials containing oxid of tin.



tltillhllt` t STATES PATENT ClllllltE. p

' HANS GGLDSCHMIDT, OF ESSEN-ONTI3IE-RUHR, GERMANY.

PROGESS 0F M.A.NUFACTURING STANNIC CHLORID FROM MATERIALS CONTAINING OXID 0F TIN.

montana.

No Drawing.

Specification of Letters Patent.

Application filed February 5, 1908.

Patented Alle'. et, 1914:. serial No. 414.435.

To 17X trimm it may concern.'

lle it known that I, IluNs GoLnsffnM/ m'n a subject of thetKingot' Prussia and (lernuln Emperor, and a resident of Essen-onthe-lluhr, Germany, have invented certain new and useful Improveuleuts in the Process of )'lanufacturing Stannic Chlorid :from hilaterials (flontaiuing (.)xid of Tin, of which the followingP is an exact specilhfation.

It is well known that anhydrtuls metallic chloride. as lthose of chromium, aluminimn, silicon, tin, ete., are made according to )erstedt (Oversight over' Salen' aka/ferma Sfr/Static Fer/1(nu/Unger 25) b v mixingl the oxids` with carbon and passing chlorin over this mixture when at a red heat. l3nt this ,method has always been very dillicult to carry out in practice, as iron apparatus could not be employed on account ot' beine' `considerabllty attacked by chlorin at this temperature. One had to make lthe appiiratus otret'ractory uxaterials which, as it is known, cannot conveniently be tightened against leakage ot chlorin at a high temperature and which, besides, show the other known drawbaclos. It therefore must be considered a technical improvement it' it is possible to make one ot' these anhydrous chlorids, in this ase stannic chlorid. from the oxid at a loul tenu'ierature iu such a manner that the operation maT be carried ont in metallic vessels, without separating the metal in a regalino state. This result is 'attained according to my invention by dividing' the process into two steps. The niatcrials containing oxid ot tin are reduced at a low tcnu'ierature in such a manner that the metallic tin is prtuluced in a tinely divided state. v 'lhc essential part ot' this method is already linowrn. but there arises the qnestion` how to bring out this finely divided tin. If the reduction is carried out with some care, that is to say, at a temperature ot 9004000", adding a sullicient quantity ot' carbon (without too great an excess), a relatively solid, porous, cougrlolgiulated mass is obtained, and practically none of the tin will be lost by pass-ine,V into the slag. ln t'act very little or no slingf is formed in the process if these conditions are closely adhered to. lly many exmrizuents it has been shown that; the `finely divided tin contained in this mass` Amay be tanstornied into stannic chlorid by the direct ,action ot' chlorinA It has been proved advantageous to subgect this mass directly to chlorination instead oft connnuutnur it, as the chlorln penetrates much bet- `ter into this porous uniss than into the pou der, the surface represented by the latter beingl a much smaller one. The porous mass from the caleiuinp; furnace may be innuediately brought into iron apparatus in which it is cooled and then acted upon by gaseous chlorin, It will be advantageous to work this part ot the process in closed vessels under a pressure of about l atmosphere above atmospheric in order to convert all the tin contained in the mass into chlorid. The current ot' chloriu must he so regulated that the temperature in the apparatusl remains below 100') C., in order to be sure that the iron will not be attacked. It is obvious that the chlorination should he performed, it"

anhydrous chlorid is desired. in a perfectly dry vessel, and that hoth the chlorin and the porous tin-lnildinef mass should he pcrt'cctly dry. as the presence ot` u'atcr will cause the chlorin to act upon iron u(both in the mass. and the walls of the vessel) and on man v ot the impurities presenti. This process is especially suited For using oxids ot tin and rich tin ores, the impurities ot' which, such as iron. copper, lead, bismuth compounds and ,enligne -u'ill remain behind, thc. anhydrous chlorid ot' tin being run oil', distilled or sucked otl" from the apparatus by decreasinei the pressure. The result obtained by thisinetlu'ul ot' chloriuatixnqr the finely divided tin is extremely ,goed and the output will be practically quantitative.

Although it seems a simple matter tio re duce all thc tin u'eseut. at a low tenuierature into metallic tin` the avoidance of oxidation ot the tiuelv divided tin always presents in practice, certain dillicultics, But it has been found that even those quantities which may have been reoxidized or which may not have been reduced will be transfornu'd into stan` nic chlorid ou account, firstly ot' the presence of a sntlicient quantity ot carbon which will reduce any oxid present during;r the chlorination, and, secondly, on account of the. local increases of tenuuirature which will probabi)r take place in the interior of the mass during the chlorination, at which increased ten'ipcratlne transl'orrnation ol the oxid or protoxid of tin into chlorid will take place. ln the apparatus itself there may be, at certain fioints, temperatures of considerably above 100D l., at which temperature the iron 4hydrated tinoxid obtained in an impure state from the Wash Waters'of silk dyers woiks.) containing about 65 per cent.- Sn, are (mixed with 11 of anthracite coal and are heated in a inutile for about 6 hoursl at a ing the oxid of tin at a suiiiciently low teini perature to produce a porous mass containr ing metallic tin and then lsubjecting-the latcess to produce a porous masscontaiiiing metemperature of SOO-()o C. There are obtained about 16 kg. of a conglobulated,-po rous mass from. which are obtained, by the action of chlorin,.74.5 kg.` anhydrous stannicl chlorid, (corresponding to 34.0 kg. Sn). The residue consists of a conglobulatedmassf Weighing about .13.4 kg. which containsl about 2.48 per cent. of tin.

What l claim is:

1. The method of manufacturing drous chlorid of tin from materials contain-l ing oxid of tin` which comprises first"reduc; ing the oxid of tin under conditions to pro-j duce a porous masscontainingthe tin-1n a. metallic state, and then subjecting the latterl to the action of clilorin gas. v

2. The method of manufacturing anhydrous chlorid .of tinv from materials contain-`i ing oxid of tin. .which consists in rst reduc-I ter tothe action. of chlorin gas.

3. The method of manufacturing anhy drous chlorid of tin from materials contain-` ing oxid ot tin, v vhich com rises first reducing the oxid of tm at a su 'cientlylow temperature to produce a porous mass containing metallic tin in a finely divided state and then subjecting the latter to the-action of chlorin gas. f'

4. The method of manufacturing anhydrous chlorid of tin'froin materials containing oXid of tin-,Which com rises first reducing the oxid of tin at a su ciently low tempeiature by means of carbon in a small'excess to produce a porous mass containing 1 metallic tin in a finely divided state and then.

subjecting' the latter to the action of chloiin Gas. Y D 5. The'metho of .manufacturing anhydrous chlorid o tinfrom' materials containing oxid of tin, which comprises lfirst reducing the oXid ot tin ata suiiiciently low temperature to produce a porous mass ,containing metallic tin vand then subj ecting the latter to the action-of chlorin gas under pressure.v 6. The method of manufacturing anhydrous chlorid of tin iirom materials containing' oxid ot tin-which comprises' iirst. reducing the otid ot tin at a temperature not materially above 1000o to produce aporon's mass containing metallic tin in a finely divided state and lthen subjecting the latter to-ftlle action of c hlorin gas under rassure.

7. The method of' manu acturing anhyfui drous clilorid of tin from materials containing oxid of tin,'whieh comprises first reducing the oxid of tin at a suiiicientlyloiv temperature by means .of carbon in .a small eitcess to a permeable mass containing metallic tin in a finely divided state and then' subjecting the latter to the action vof chlorin gas under` ressure.

v'8. T e method of .manufacturing anhydrouschlorid of tin from materials 'containing oxid oftin', which comprises first reducing the oXidof tin at asufiiciently low tem-l perature tol a permeable vmass containing mei tallic tin and their subjecting the latter to the' action of chlorin gas under pressure, at'v a temperature not greatly in excess of 1000 C. .9..Themethod 'of manufacturinganhydrous chlorid of -tin from materials containingoxid of tin, Which comprises iirst reducing the oXid of tin at a sufficiently.- loiv temeraturef to produce a porous mass containing metallic tin in a. finely divided ystate and.

.then subjectin ythe latter tothe action of i chlorin gas un er pressure at a temperature not greatly--exceeding- '100 C. l v 10.. The method of manufacturing tallic tin in a' finely ldivided state 'and then subjecting the latter to the action of clilorin l anhydrous chlorid o'tin from materials contain: ing oXid of tin, which com rises firstv reducteingas under pressure at a temperature not greatly in excess of 100' C;

11. The method of manutacturinganhydrous chlorid of tin from materials containing 'oxid of tin, which comprises first-reducing the oXid of tin at a temperature sujlli'- cientlylow to avoid the formation of slags andafterivard subjecting the mass `to the action'offchlorin gas. l

12.4 The method of manufacturinganhydrous chlorid 03E tin from materials contain- 'ing oxid oftin, which comprlses first reducing. the oXid 4ofl tin at a temperature sufiiciently 'low to avoid thc formation offslags to metallic tin in a'iioii-regulino state and'.

afterward" subjecting the -inass to the action of chlorin gas.

13. The method of manufacturing anhydrous chlorid of'tin from materials containi ing oxid of tin, whichcoinprisesirst reducing "tlie cXid of tinjat LV-temperature suilicicntly lfnv to avoid the formation of slugs by means of carbonin a small excess. to me.- 'tallic tin iii 'a non-,regulinc state and altervWard 'subjecting the mass to the action ot chlori'n'gas. y 4.

14. The method of manufacturing anhyiat.

iso

drous chlorid of tin 'from materials containing oxid ot tin, which comprises first reduca ing the oxid of tin at a temperature suiiiciently lou' to aroid the -t'orn'ifttion of sings and afterward Sul'ijecting the mass to the action oit chlorin gas under pressure.

15. The method of manufacturing anhydrous ehlorid. of tin from materials containing oxid of tin, which compriaes first reduc4 ing the oxid ot tin at a tempe'ature sufficient ly low to avoid the formation oi slugs to metallic tin in a nonreguline State and afterward subjecting; the mass to the action ot' ehlorin gas under pressure.

16. The method of manut'zurtnringanhydrous chlorid ot." tin trom materiale containingoxid of tin. which comprises first reducing the oxid ot tin at a temperature nutticiently low to avoid the formation ot slags by means;I of carljionin a small excess to metallic tin in a non-reguline state and afterward subjecting the mass to the action ot chlorin gas under pressure.

17. The method of Inamltaeturing;r anhydrone chlorid of tin `from materials containing oxid of tin, which comprises tirety reduring,r the oxid ot' tin at a temperature sut iiciently low to avoid the formation of: Stags and afterward subjecting' the mass to the Aaction, et' chlorin gas under prcsaure atV a temperature not greatly exceeding C.

i8. The method o't manutacturinar anhy droua ehlorid of tin from materials containing oxid oi tin, which f :omprises first reducing the oxid of tin ai a, temperature sultciently low to avoid the formation ot Shiga to metallic tin in a, non-reguliuc state and afterward auloj(actingT the mass to the action of chlorin gas under preasnre at a temperature not Igreatly exceeding 100 lil. The method ot' manufacturing anhydrous chlorid of tin troni materials containing artid ot tin, which comprises .first reducing! the oxid o't` tin at a tenijurature Suffcieutly low to avoid the formation ot' Slaan hy means: ot' carhon in a small exceas to motallic tin in a nou-reguline state and after ward enhjecting the maas to the action of chlorin gas under pressure at a temperature not lfrreatly exceeding 100" C.

20. A. proco't' making anhydrous Stain nic chlcrid which commises subjecting material. containing` tin oxidV to a reduction proceas: at; euch a temperature as to avoid the At'ormatimi of Slag` and the. passage of tin into slag. then treatingV the product ot the reduction in a drystate and .free :from slag and in dry tanks to a current of dry chlorin. j

2i. A procesa ot making anhydrous stannie chlorid which comprisessubjecting material containing tin oxid to a reduction procese at euch a temperature as to avoid the formation of slag and the passage ot tin into slag, then treat-ing the product of the reduction in a dry state and tree trom slag,r and in dry tanks to a current ot dry chlorin under. pressure.

Q2. A processoI ot making anhydrous stan nio chlorid which eozcprisea subjecting` material t attaining tin oxid to a reduction process atsuch a temperature as to avoid the formation of slag and the passage oi tin into slag, then treating the product of the reduction in a dry state and free from slagI and in dry tanks to a current of dry chiorin.

23. In the manufacture ot' stannic chlorid, the step ot reacting upon a spongy, pervious mass containingr metallic tin, with chlorin gas.

l'n the manufacture ot `aiannicchlorid, the step ot reacting upon a spongy, pervious mas-5 containing metallic tin, and impurities not readily attacked by chlorin with chlorin gas. j

Q5. In the manufacture of otannic chlorid, the step ot.' reacting,Y upon a spongrj, pervious masia containing metallic tin, and other metals, the chloride of which are not readily soluble 4in anhydroua stannic chlorid, with chlorin gas.

'2(3. ln the manutacture of stannc chlord., the step ot' reacting upon a spongy, perviene mane containing, metallic tin7 with chlorin gas. under pressure.

2T. In the manufacture ot Slauuic chlorid, the step of reacting upon a spongry. pervious n ass containing' metallic tin, with chlorin gras, under a pressure of about one atmosphere ahove normal. l

[n the imlmrfacture ot stannic chlorid, the .step ot reactingl upon a spong'y, pcrvinua mass containing` metallic tin, with chlorin gras, at a temj'ierature `not considerably ahovc 100o (Y.

29. In the manufacture of Sta nnic chlorid, the step ot' reacting upon a dry, spongfy, pcrvious mass containing; metallictin, with dry chlorin gas, at a temperature not ma terially above ,i000 (ai.

fit). ln the manufacture of: Stannic chlorid, the Step ot reacting: upon a dry, epongy, pervious maas containing metallic tin, with dry chlorin aan, at a temperature not con- Sider-ably ahove 100 C., andunder pressure,

Si. A. process of making" stannic chlorid which comprisca reducing tin oxid to a pervious. epong'y maas4 containingV metallic tin, and there: fltcr reactingr thereupon with chlorin gas. l 5&2. A proceseA of making anhydrous stannie chlorid which compriaee` subjectiony material containingr tin oxid to a reduction, process at such a temperature as to avoid the formation ot slag and the passage ot tin into slag, and thereafter treating' the product of thie reduction in a dry State and free from Slag: and in dry tanks to a current ot dry chlorin. at a temperature not greatly exceeding' 'i000 C.

A process of making anhydrous stannic ehlorid which comprises subjectingma-A teriai containii'ig tin oXid to a reduction process at such temperature as to avoid the formation of. slag `md the passage of tin into slag and thereafter treating the. product of this reduction in a dry state 'and free u nie chlorid which comprises subjecting material containing tin oXidrto a reduction process at such a temperature as to avoid the formation of slag and the passage of tm into slag, and thereafter treating theprodnct ofv this reduction with chlorin gas.

A process of converting an oXid of an element into a chlorid, which comprises reacting on said oXid with a reducing agent at a temperature sufficiently low to form a porous, perrious mass containing the element in a finely divided state, and to avoid 'the formation of a slag; and thereafter treating said porous, pervious Lnass with a chloridizing gas at a temperature at which said gas attacks said element.

3G. A process of converting an oxid of an clement into a chlorid-, which comprises reacting on said oxid with a. reducing agent at a temperature sufficiently loW to form aporous, pervious mass containing the element in a finely divided state, and to avoid the formation ofl a slag; and thereafter treating said porous, pervious mass with a chloridizing gas under pressure, and at-a temperaturevat which said gas attacks said. element.

3T. A process of converting an oxid of an a temperaelement into a chlorid, which comprises reacting on said oxid with a reducing agent at a temperature sufficiently low to form a porous, pervious mass containing the element in a finely divided state, and to avoid the formation of a slag; thereafter treating said porous, pervious mass with a chloridizing gas at a temperature at which said gas atacks said element, and thereafter separating the chiorid from thc other material remaining.

38. A process of converting an oxid of an element into a ehlorid, which vcomprises reacting `on said oXid With a reducing agent at a temperature suticiently low to form a porous, perrous mass containing the eiement in a iinely divided state, and to avoid the formation of av slag; and thereafter treating said porous, pervious mass with chlorin gas atv a temperature at Which said gas attacks said element.

S9. A process vof converting an oXid of an element into a halogen compound, Whichcomprises reacting on said oXid With a reducing agent at a temperature sufiiciently low toform a porous, pervious mass containing the element in a inely dlvlded state,

and to avoid the formation of a slag; and thereafter treating said porous, pervious mass Wih a. halogenizing agent at a temperature at which said agent attacks said element.

Signed at New York, in the county of lNew York, and State of New York, this 13th day of December, A. D. 1907. p

HANS GOLDSCHMlDT. Vvitnesses HUBERT E. ROGERS,

F. H. I-linsoI-ILAND. 

